US4710437A - High rate metal oxyhalide cells - Google Patents

High rate metal oxyhalide cells Download PDF

Info

Publication number
US4710437A
US4710437A US06/818,072 US81807286A US4710437A US 4710437 A US4710437 A US 4710437A US 81807286 A US81807286 A US 81807286A US 4710437 A US4710437 A US 4710437A
Authority
US
United States
Prior art keywords
metal
cell
complexes
cobalt
iron
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US06/818,072
Inventor
Narayan Doddapaneni
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Enersys Advanced Systems Inc
Original Assignee
Honeywell Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Honeywell Inc filed Critical Honeywell Inc
Priority to US06/818,072 priority Critical patent/US4710437A/en
Application granted granted Critical
Publication of US4710437A publication Critical patent/US4710437A/en
Assigned to ALLIANT TECHSYSTEMS INC. reassignment ALLIANT TECHSYSTEMS INC. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: HONEYWELL INC. A CORP. OF DELAWARE
Assigned to CHASE MANHATTAN BANK, THE reassignment CHASE MANHATTAN BANK, THE PATENT SECURITY AGREEMENT Assignors: ALLIANT TECHSYSTEMS INC.
Assigned to ALLIANT TECHSYSTEMS INC. reassignment ALLIANT TECHSYSTEMS INC. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: JPMORGAN CHASE BANK (FORMERLY KNOWN AS THE CHASE MANHATTAN BANK)
Assigned to BANK OF AMERICA, N.A. reassignment BANK OF AMERICA, N.A. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ALLANT AMMUNITION AND POWDER COMPANY LLC, ALLIANT AMMUNITION SYSTEMS COMPANY LLC, ALLIANT HOLDINGS LLC, ALLIANT INTERNATIONAL HOLDINGS INC., ALLIANT LAKE CITY SMALL CALIBER AMMUNTION COMPANY LLC, ALLIANT SOUTHERN COMPOSITES COMPANY LLC, ALLIANT TECHSYSTEMS INC., AMMUNITION ACCESSORIES INC., ATK AEROSPACE COMPANY INC., ATK AMMUNITION AND RELATED PRODUCTS LLC, ATK COMMERCIAL AMMUNITION COMPANY INC., ATK ELKTON LLC, ATK LOGISTICS AND TECHNICAL SERVICES LLC, ATK MISSILE SYSTEMS COMPANY, ATK ORDNACE AND GROUND SYSTEMS LLC, ATK PRECISION SYSTEMS LLC, ATK TECTICAL SYSTEMS COMPANY LLC, ATKINTERNATIONAL SALES INC., COMPOSITE OPTICS, INCORPORTED, FEDERAL CARTRIDGE COMPANY, GASL, INC., MICRO CRAFT INC., MISSION RESEARCH CORPORATION, NEW RIVER ENERGETICS, INC., THIOKOL TECHNOGIES INTERNATIONAL, INC.
Anticipated expiration legal-status Critical
Assigned to ALLIANT TECHSYSTEMS INC. reassignment ALLIANT TECHSYSTEMS INC. RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: BANK OF AMERICA, N.A.
Assigned to ENERSYS ADVANCED SYSTEMS INC. reassignment ENERSYS ADVANCED SYSTEMS INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ALLIANT TECHSYSTEMS INC.
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00Primary cells; Manufacture thereof
    • H01M6/14Cells with non-aqueous electrolyte
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • H01M4/663Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/9008Organic or organo-metallic compounds
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Definitions

  • the present invention relates generally to the field of non-aqueous electrochemical cells and, more particularly to a class of catalysts for the reduction of oxyhalide depolarizers such as SOCl 2 and SO 2 Cl 2 in such cells.
  • the electrolyte is normally composed of a solute which is commonly a metal salt or a complex metal salt of the anode metal dissolved in a compatible non-aqueous solvent depolarizer such as SO 2 , SOCl 2 , or SO 2 Cl 2 .
  • a compatible non-aqueous solvent depolarizer such as SO 2 , SOCl 2 , or SO 2 Cl 2 .
  • An inert cathode, usually of carbon black, is also used in such cells.
  • improved catalysts for the reduction of oxyhalide depolarizes such as SOCl 2 and SO 2 Cl 2 are provided which are easier to prepare and less expensive than phthalocyanine complexes and which are generally more stable in the cell environment.
  • These catalysts include certain marcocyclic complexes of Schiff's base prepared by the reaction of an aldehyde with a primary diamine.
  • the preferred embodiments include mononuclear metal macrocyclic complexes made from salicylaldehyde and o-phenylenediamine of a structure such as ##STR1## and binuclear metal macrocyclic complexes of 5-methyl isophthalaldehyde and 1,3-diaminopropane having a structure such as ##STR2## where M or Me represents a metal selected from the group consisting of iron and cobalt and m and n represent integers.
  • FIG. 1 is a graphical representation of the discharge characteristics of a Li/SOCl 2 cell employing prior art catalysts cobalt phthalocyanine (CoPc) and iron phthalocyanine (FePc) dissolved in the electrolyte compared with the uncatalyzed baseline.
  • CoPc cobalt phthalocyanine
  • FePc iron phthalocyanine
  • FIG. 2 is a graphical representation showing the discharge characteristics of a Li/SOCl 2 cell using mononuclear CoSB catalyst compared with the uncatalyzed baseline.
  • FIG. 3 is a graphical representation of polarization characteristics of a Li/SOCl 2 cell using binuclear metal complexes FeMac and CoMac of the invention
  • FIG. 4 is a graphical representation of the discharge characteristics of a cell of FIG. 2 at 23° C. and 63° C. with and without CoSB.
  • Example 1 The process of Example 1 was repeated except that iron chloride was substituted for cobalt chloride of Example 1.
  • Examples 1 and 2 produced binuclear metal marcocyclic complexes CoMac and FeMac, respectively, of the following structure: ##STR3## where M represents iron or cobalt and m and n are integers.
  • Example 3 was repeated substituting iron acetate for the cobalt acetate.
  • Table 1 and 2 show a comparison of discharge characteristics of cells using a prior art catalyst, the catalyst of Example 3, and no catalyst.
  • FIG. 1 shows the discharge characteristics of prior art cells using cobalt phthalocyanine (CoPc) and iron phthalocyanine (FePc) catalysts dissolved in the electrolyte. It should be noted that the FePc exhibits a somewhat higher catalytic activity.
  • FIGS. 2-4 show data derived using the catalysts of the present invention.
  • FIGS. 2-4 the discharge characteristics of Li/SOCl 2 cells catalyzed by various metal macrocyclic complexes are compared to an uncatalyzed cell. All catalyzed cells showed substantial improvement in both cell voltage and specific cathode capacity over the uncatalyzed cell. These complexes have shown as good or better catalytic activity for the reduction of SOCl 2 than the iron phthalocyanine catalyst.
  • FePc showed the best catalytic activity, whereas, cobalt tetraphenylporphyrin (CoTPP) and cobalt Schiff's base complexes (CoSB) possess superior catalytic activity for SOCl 2 reduction than the iron complexes of these macrocyclic rings.
  • CoTPP cobalt tetraphenylporphyrin
  • CoSB cobalt Schiff's base complexes
  • the operating temperature also appears to influence the catalytic activity as shown in Table 2.
  • the cell performance improved with catalyzed cells irrespective of operating temperatures and current densities.
  • the catalytic activity of cobalt Schiff's base complex is rather reduced but the significance of this behavior is not yet understood.
  • one of the factors could be the specific interaction of the CoSB complex with carbon cathode surface.
  • a better way of impregnating the complex onto carbon should show better results since the performance of cells with this catalyst is drastically improved at high operating temperatures.
  • the catalyst stability is projected to be responsible for the superior performance at high operating temperatures.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inert Electrodes (AREA)

Abstract

Improved catalysts for the reduction of oxyhalide depolarizers such as SOCl2 and SO2 Cl2 in active-metal non-aqueous cells are provided which are easier to prepare and less expensive than phthalocyanine complexes and which are generally more stable in the cell environment. These catalysts include certain macrocyclic complexes of Schiff's base prepared by the reaction of an aldehyde with a primary diamine. The preferred embodiments include mononuclear metal macrocyclic complexes made from salicylaldehyde and o-phenylenediamine and binuclear metal macrocyclic complexes of 5-methyl isophthalaldehyde and 1,3-diaminopropane.

Description

This application is a continuation of application Ser. No. 652,362, filed Sept. 19, 1984 now abandoned.
BACKGROUND OF THE INVENTION
The invention herein described was made in the source of or under a contract or subcontract thereunder with the Department of the Army.
FIELD OF THE INVENTION
The present invention relates generally to the field of non-aqueous electrochemical cells and, more particularly to a class of catalysts for the reduction of oxyhalide depolarizers such as SOCl2 and SO2 Cl2 in such cells.
DESCRIPTION OF THE PRIOR ART
Much work has been done in the field of high energy battery systems utilizing highly reactive anode materials such as alkali or alkaline earth metals in combination with a non-aqueous electrolyte. The electrolyte is normally composed of a solute which is commonly a metal salt or a complex metal salt of the anode metal dissolved in a compatible non-aqueous solvent depolarizer such as SO2, SOCl2, or SO2 Cl2. An inert cathode, usually of carbon black, is also used in such cells.
The potential of electrochemical couples, such as those mentioned above as high rate, high-power batteries, has not been fully realized mainly because of excessive cathode polarization particularly at high discharge rates and low operating temperatures. This causes a deterioration of cell performance after a short period of operation. For this reason, much research has been conducted concerning the development of additives such as catalysts to reduce the cathode depolarizer, thereby improving the rate capability of the cathodes.
Some improvement in the rate capability of these carbon cathodes has been achieved by doping them with metals such as platinum or metal halides. However, high amounts of the metals or metal halides are required to effectively increase the rate capability of cells such as Li/SOCl2 cells. Also, the cell performance of these dopants deteriorates with thinner electrodes and at the higher temperatures required for certain applications. More recently, metal-phthalocyanine complexes have been shown to possess significant catalytic activity for the electrochemical reduction of solvent depolarizers such as thionyl chloride or sulfural chloride, thereby increasing cell capacity. Examples of such are found in U.S. Pat. Nos. 4,252,875 and 4,405,693. The need still exists for the provision of catalyzed cathodes for cells such as Li/SOCl2 cells which are stable and effective over a wide temperature range and which are sufficiently stable in the cell to be used in both active and reserve configurations.
SUMMARY OF THE INVENTION
By means of the present invention, improved catalysts for the reduction of oxyhalide depolarizes such as SOCl2 and SO2 Cl2 are provided which are easier to prepare and less expensive than phthalocyanine complexes and which are generally more stable in the cell environment. These catalysts include certain marcocyclic complexes of Schiff's base prepared by the reaction of an aldehyde with a primary diamine. The preferred embodiments include mononuclear metal macrocyclic complexes made from salicylaldehyde and o-phenylenediamine of a structure such as ##STR1## and binuclear metal macrocyclic complexes of 5-methyl isophthalaldehyde and 1,3-diaminopropane having a structure such as ##STR2## where M or Me represents a metal selected from the group consisting of iron and cobalt and m and n represent integers.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a graphical representation of the discharge characteristics of a Li/SOCl2 cell employing prior art catalysts cobalt phthalocyanine (CoPc) and iron phthalocyanine (FePc) dissolved in the electrolyte compared with the uncatalyzed baseline.
FIG. 2 is a graphical representation showing the discharge characteristics of a Li/SOCl2 cell using mononuclear CoSB catalyst compared with the uncatalyzed baseline.
FIG. 3 is a graphical representation of polarization characteristics of a Li/SOCl2 cell using binuclear metal complexes FeMac and CoMac of the invention;
FIG. 4 is a graphical representation of the discharge characteristics of a cell of FIG. 2 at 23° C. and 63° C. with and without CoSB.
DESCRIPTION OF THE PREFERRED EMBODIMENTS Catalyst Preparation
The syntheses of FeMac and CoMac were carried out using the method of Pilkington et al, Australian Journal of Chemistry Vol. 23, 2225 (1970). The syntheses of CoSB and FeSB were carried out using a method described in Jahnke et al, Topics in Current Chemistry, Vol. 1, 133 (1979).
EXAMPLE 1
A solution of 5-methyl isophthalaldehyde (0.05 mole) dissolved in the minimum volume of boiling methanol was added to a suspension formed by mixing 1,3-diaminopropane (0.05M) with a saturated solution of cobalt chloride in methanol. The mixture was heated under reflux for 1 hour. Methanol was removed by boiling at atmospheric pressure. The product was poured into ten times its volume of tetrahydrofuran. The product was filtered, washed with water and dried.
EXAMPLE 2
The process of Example 1 was repeated except that iron chloride was substituted for cobalt chloride of Example 1.
The process of Examples 1 and 2 produced binuclear metal marcocyclic complexes CoMac and FeMac, respectively, of the following structure: ##STR3## where M represents iron or cobalt and m and n are integers.
EXAMPLE 3
A solution of salicylaldehyde (0.05M), o-phenylenediamine (0.05M) and cobalt acetate (0.025M) was refluxed in ethanol for about 30 minutes. The resulting product was washed with cold methanol and dried at 120° C.
EXAMPLE 4
Example 3 was repeated substituting iron acetate for the cobalt acetate.
The structure of the complexes formed in Examples 3 and 4 known as CoSB and FeSB, respectively, was as follows: ##STR4##
Performance of Catalyst in Cells
Table 1 and 2 show a comparison of discharge characteristics of cells using a prior art catalyst, the catalyst of Example 3, and no catalyst.
              TABLE 1                                                     
______________________________________                                    
DISCHARGE CHARACTERISTICS OF Li/SOCl.sub.2 CELLS                          
WITH VARIOUS CATALYSTS WITH A CONSTANT                                    
CURRENT DENSITY OF 30 MA/cm.sup.2 AT 23° C.                        
                Cell Voltage                                              
                           Discharge Life                                 
Catalyst        (V)        (Minutes)                                      
______________________________________                                    
None            2.92       34                                             
Iron Phthalocyanine                                                       
                3.30       52                                             
(FePc)                                                                    
Mononuclear Couples                                                       
                3.30       70                                             
with Schiff's Base                                                        
(CoSB)                                                                    
______________________________________                                    
 ELECTROLYTE = (0.5 M LiAlCl.sub.4 + 1.0 M                                
 CATHODE THICKNESS = 1.0 millimeter                                       
                                  TABLE 2                                 
__________________________________________________________________________
DISCHARGE CHARACTERISTICS OF Li/SOCl.sub.2 CELLS                          
WITH AND WITHOUT COSB COMPLEX AT A CONSTANT                               
CURRENT LOAD OF 10 MA/cm.sup. 2 AT DIFFERENT                              
OPERATING TEMPERATURES                                                    
-32° C. -18° C.                                             
                         23° C.                                    
                                  63° C.                           
     Voltage at                                                           
               Voltage at                                                 
                         Voltage at                                       
                                  Voltage at                              
     50% DOD                                                              
           DOD 50% DOD                                                    
                     DOD 50% DOD                                          
                               DOD                                        
                                  50% DOD                                 
                                         DOD                              
Catalyst                                                                  
     (V)   (min)                                                          
               (V)   (min)                                                
                         (V)   (min)                                      
                                  (V)    (min)                            
__________________________________________________________________________
None 2.70  55  2.80  80  3.12  105 3.36  164                              
CoSB 2.72  60  2.94  90  3.39  182 3.44  193                              
__________________________________________________________________________
FIG. 1 shows the discharge characteristics of prior art cells using cobalt phthalocyanine (CoPc) and iron phthalocyanine (FePc) catalysts dissolved in the electrolyte. It should be noted that the FePc exhibits a somewhat higher catalytic activity. FIGS. 2-4 show data derived using the catalysts of the present invention.
In FIGS. 2-4, the discharge characteristics of Li/SOCl2 cells catalyzed by various metal macrocyclic complexes are compared to an uncatalyzed cell. All catalyzed cells showed substantial improvement in both cell voltage and specific cathode capacity over the uncatalyzed cell. These complexes have shown as good or better catalytic activity for the reduction of SOCl2 than the iron phthalocyanine catalyst. In the case of metal pthalocyanine catalysts, FePc showed the best catalytic activity, whereas, cobalt tetraphenylporphyrin (CoTPP) and cobalt Schiff's base complexes (CoSB) possess superior catalytic activity for SOCl2 reduction than the iron complexes of these macrocyclic rings. Electronic charage density on the central metal ion, extent of orbital overlapping backbonding and the nature of the specific interaction of the complex with the carbon surface, are some of the factors that can influence the catalytic activity of these complexes for the reduction of SOCl2. In the case of the binuclear macrocyclic complexes the iron couples appear to be superior.
Whereas in Examples 1 and 2 the primary diamine utilized was 1,3-diaminopropane, it will be appreciated that other primary alkyl diamine compounds can be used. The reactions of the alkyl diamines are sufficiently similar and well enough understood that such substitutions might well occur to one skilled in the art.
The operating temperature also appears to influence the catalytic activity as shown in Table 2. In general, the cell performance improved with catalyzed cells irrespective of operating temperatures and current densities. At low operation temperatures, however, the catalytic activity of cobalt Schiff's base complex is rather reduced but the significance of this behavior is not yet understood. However, one of the factors could be the specific interaction of the CoSB complex with carbon cathode surface. A better way of impregnating the complex onto carbon should show better results since the performance of cells with this catalyst is drastically improved at high operating temperatures. The catalyst stability is projected to be responsible for the superior performance at high operating temperatures.

Claims (6)

The embodiments of the invention in which an exclusive property or right is claimed are defined as follows:
1. In an non-aqueous electrochemical cell system having an active metal anode, a cathode and a non-aqueous electrolyte having an oxyhalide depolarizer, the improvement comprising:
a catalyst for the reduction of said oxyhalide depolarizer comprising a metal complex of Schiff's base, said Schiff's base being selected from the group consisting of macrocyclic complexes of 5-methyl isophthalaldehyde and 1,3-diaminopropane wherein the metal in said metal complex is selected from the group consisting of iron and cobalt and wherein said metal complex is binuclear.
2. The cell of claim 1 wherein said metal is cobalt.
3. The cell of claim 1 wherein said metal is iron.
4. In a non-aqueous electrochemical cell having a lithium anode, a carbon cathode and a non-aqueous electrolyte comprising LiAlCl4 salt is SOCl2 depolarizer solvent the improvement comprising:
a catalyst for the reduction of said oxyhalide depolarizer comprising a metal complex of Schiff's base, said Schiff's base being selected from the group consisting of macrocyclic complexes of 5-methyl isophthalaldehyde and 1,3 diaminopropane wherein the metal in said metal complex is selected from the group consisting of iron and cobalt and wherein said metal complex is binuclear.
5. The cell of claim 4 wherein said metal is cobalt.
6. The cell of claim 4 wherein said metal is iron.
US06/818,072 1984-09-19 1986-01-13 High rate metal oxyhalide cells Expired - Lifetime US4710437A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US06/818,072 US4710437A (en) 1984-09-19 1986-01-13 High rate metal oxyhalide cells

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US65236284A 1984-09-19 1984-09-19
US06/818,072 US4710437A (en) 1984-09-19 1986-01-13 High rate metal oxyhalide cells

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US65236284A Continuation 1984-09-19 1984-09-19

Publications (1)

Publication Number Publication Date
US4710437A true US4710437A (en) 1987-12-01

Family

ID=27096282

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/818,072 Expired - Lifetime US4710437A (en) 1984-09-19 1986-01-13 High rate metal oxyhalide cells

Country Status (1)

Country Link
US (1) US4710437A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4888255A (en) * 1987-06-24 1989-12-19 Hitachi Maxell, Ltd. Non-aqueous electrochemical cell
US4921586A (en) * 1989-03-31 1990-05-01 United Technologies Corporation Electrolysis cell and method of use
US4921585A (en) * 1989-03-31 1990-05-01 United Technologies Corporation Electrolysis cell and method of use
US5358803A (en) * 1992-05-06 1994-10-25 Eic Laboratories, Inc. Catalyzed cathodes for electrochemical cells
WO2003083967A2 (en) * 2002-03-27 2003-10-09 Regenesys Technologies Limited An electrode for the reduction of polysulfide species

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3595702A (en) * 1968-07-16 1971-07-27 Varta Gmbh Active mass for galvanic elements and frocess of making the same
US4128702A (en) * 1977-11-25 1978-12-05 Teijin Limited Cell with N,N-bis (substituted phenyl)-4,4- dipyridinium salt depolarizer
US4181779A (en) * 1979-01-30 1980-01-01 Bell Telephone Laboratories, Incorporated Cell using halogen reactive material such as organo-metallic polymer
US4252875A (en) * 1980-04-14 1981-02-24 Honeywell Inc. Electro-catalysts for the cathode(s) to enhance its activity to reduce SoCl2 in Li/SoCl2 battery
US4293623A (en) * 1980-07-03 1981-10-06 Exxon Research & Engineering Co. Electrolytes for alkali-metal electrochemical devices
US4393125A (en) * 1980-04-21 1983-07-12 Medtronic, Inc. Battery cathodes
US4405693A (en) * 1981-10-05 1983-09-20 Honeywell Inc. High rate metal-sulfuryl chloride batteries
US4469763A (en) * 1983-10-21 1984-09-04 Tracer Technologies, Inc. Lithium oxyhalide battery with cathode catalyst

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3595702A (en) * 1968-07-16 1971-07-27 Varta Gmbh Active mass for galvanic elements and frocess of making the same
US4128702A (en) * 1977-11-25 1978-12-05 Teijin Limited Cell with N,N-bis (substituted phenyl)-4,4- dipyridinium salt depolarizer
US4181779A (en) * 1979-01-30 1980-01-01 Bell Telephone Laboratories, Incorporated Cell using halogen reactive material such as organo-metallic polymer
US4252875A (en) * 1980-04-14 1981-02-24 Honeywell Inc. Electro-catalysts for the cathode(s) to enhance its activity to reduce SoCl2 in Li/SoCl2 battery
US4393125A (en) * 1980-04-21 1983-07-12 Medtronic, Inc. Battery cathodes
US4293623A (en) * 1980-07-03 1981-10-06 Exxon Research & Engineering Co. Electrolytes for alkali-metal electrochemical devices
US4405693A (en) * 1981-10-05 1983-09-20 Honeywell Inc. High rate metal-sulfuryl chloride batteries
US4469763A (en) * 1983-10-21 1984-09-04 Tracer Technologies, Inc. Lithium oxyhalide battery with cathode catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Jahnke, et al; Organic Dyestuffs as Catalysts for Fuel Cells, Topics in Current Chemistry 61, 133 (1970). *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4888255A (en) * 1987-06-24 1989-12-19 Hitachi Maxell, Ltd. Non-aqueous electrochemical cell
US4921586A (en) * 1989-03-31 1990-05-01 United Technologies Corporation Electrolysis cell and method of use
US4921585A (en) * 1989-03-31 1990-05-01 United Technologies Corporation Electrolysis cell and method of use
US5358803A (en) * 1992-05-06 1994-10-25 Eic Laboratories, Inc. Catalyzed cathodes for electrochemical cells
WO2003083967A2 (en) * 2002-03-27 2003-10-09 Regenesys Technologies Limited An electrode for the reduction of polysulfide species
WO2003083967A3 (en) * 2002-03-27 2004-10-28 Regenesys Tech Ltd An electrode for the reduction of polysulfide species
CN1312802C (en) * 2002-03-27 2007-04-25 里珍西斯技术有限公司 An electrode for the reduction of polysulfide species

Similar Documents

Publication Publication Date Title
US6045952A (en) Electrochemical storage cell containing a substituted anisole or di-anisole redox shuttle additive for overcharge protection and suitable for use in liquid organic and solid polymer electrolytes
US3992222A (en) Metallic sulfide additives for positive electrode material within a secondary electrochemical cell
US4064324A (en) Metal-Halogenelectrochemical cell
CA1066761A (en) Halogen complexing alcohols and nitriles
US5472807A (en) Aluminum-ferricyanide battery
JP2698340B2 (en) Electrochemical battery
KR20010012249A (en) An iron-based storage battery
CA1256938A (en) High rate metal oxyhalide cells
US4710437A (en) High rate metal oxyhalide cells
JP3081336B2 (en) Non-aqueous electrolyte secondary battery
US4346152A (en) Lithium-germanium electrodes for batteries
US4752541A (en) Electrolyte for lithium-sulfur dioxide electrochemical cell
CA1078007A (en) Metal halogen electrochemical cell
US4262065A (en) Additive for lithium batteries
US4405693A (en) High rate metal-sulfuryl chloride batteries
US4469763A (en) Lithium oxyhalide battery with cathode catalyst
US4613551A (en) High rate metal oxyhalide cells
US4751160A (en) Organic electrolyte for use in a lithium rechargeable electrochemical cell and lithium rechargeable electrochemical cell including said organic electrolyte
JPH0456079A (en) Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery thereof
US4526881A (en) Method of pretreating carbon black powder to improve cathode performance and lithium sulfuryl chloride cell including the pretreated carbon black powder
US5358803A (en) Catalyzed cathodes for electrochemical cells
US4698283A (en) Electrochemical cell having improved active life
EP0239976A2 (en) Molten salt secondary battery
CA1258107A (en) Secondary lithium cell
US4543305A (en) Method of pretreating carbon black powder to improve cathode performance and lithium sulfuryl chloride cell including the pretreated carbon black powder

Legal Events

Date Code Title Description
FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

AS Assignment

Owner name: ALLIANT TECHSYSTEMS INC., MINNESOTA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:HONEYWELL INC. A CORP. OF DELAWARE;REEL/FRAME:005845/0384

Effective date: 19900924

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 8

FEPP Fee payment procedure

Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

AS Assignment

Owner name: CHASE MANHATTAN BANK, THE, NEW YORK

Free format text: PATENT SECURITY AGREEMENT;ASSIGNOR:ALLIANT TECHSYSTEMS INC.;REEL/FRAME:009662/0089

Effective date: 19981124

FPAY Fee payment

Year of fee payment: 12

AS Assignment

Owner name: ALLIANT TECHSYSTEMS INC., MINNESOTA

Free format text: SECURITY INTEREST;ASSIGNOR:JPMORGAN CHASE BANK (FORMERLY KNOWN AS THE CHASE MANHATTAN BANK);REEL/FRAME:015201/0351

Effective date: 20040331

AS Assignment

Owner name: BANK OF AMERICA, N.A., NORTH CAROLINA

Free format text: SECURITY INTEREST;ASSIGNORS:ALLIANT TECHSYSTEMS INC.;ALLANT AMMUNITION AND POWDER COMPANY LLC;ALLIANT AMMUNITION SYSTEMS COMPANY LLC;AND OTHERS;REEL/FRAME:014692/0653

Effective date: 20040331

AS Assignment

Owner name: ALLIANT TECHSYSTEMS INC., MINNESOTA

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:BANK OF AMERICA, N.A.;REEL/FRAME:017636/0626

Effective date: 20060318

AS Assignment

Owner name: ENERSYS ADVANCED SYSTEMS INC., PENNSYLVANIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ALLIANT TECHSYSTEMS INC.;REEL/FRAME:017681/0647

Effective date: 20060518